CN113292468B - Preparation method of all-trans beta-carotene - Google Patents
Preparation method of all-trans beta-carotene Download PDFInfo
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- C07C403/00—Derivatives of cyclohexane or of a cyclohexene or of cyclohexadiene, having a side-chain containing an acyclic unsaturated part of at least four carbon atoms, this part being directly attached to the cyclohexane or cyclohexene or cyclohexadiene rings, e.g. vitamin A, beta-carotene, beta-ionone
- C07C403/24—Derivatives of cyclohexane or of a cyclohexene or of cyclohexadiene, having a side-chain containing an acyclic unsaturated part of at least four carbon atoms, this part being directly attached to the cyclohexane or cyclohexene or cyclohexadiene rings, e.g. vitamin A, beta-carotene, beta-ionone having side-chains substituted by six-membered non-aromatic rings, e.g. beta-carotene
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- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/06—Halogens; Compounds thereof
- B01J27/128—Halogens; Compounds thereof with iron group metals or platinum group metals
- B01J27/13—Platinum group metals
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- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
- B01J31/18—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes containing nitrogen, phosphorus, arsenic or antimony as complexing atoms, e.g. in pyridine ligands, or in resonance therewith, e.g. in isocyanide ligands C=N-R or as complexed central atoms
- B01J31/1805—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes containing nitrogen, phosphorus, arsenic or antimony as complexing atoms, e.g. in pyridine ligands, or in resonance therewith, e.g. in isocyanide ligands C=N-R or as complexed central atoms the ligands containing nitrogen
- B01J31/181—Cyclic ligands, including e.g. non-condensed polycyclic ligands, comprising at least one complexing nitrogen atom as ring member, e.g. pyridine
- B01J31/1825—Ligands comprising condensed ring systems, e.g. acridine, carbazole
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- B01J2231/00—Catalytic reactions performed with catalysts classified in B01J31/00
- B01J2231/50—Redistribution or isomerisation reactions of C-C, C=C or C-C triple bonds
- B01J2231/52—Isomerisation reactions
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- B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
- B01J2531/80—Complexes comprising metals of Group VIII as the central metal
- B01J2531/82—Metals of the platinum group
- B01J2531/821—Ruthenium
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- C07C2601/12—Systems containing only non-condensed rings with a six-membered ring
- C07C2601/16—Systems containing only non-condensed rings with a six-membered ring the ring being unsaturated
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Abstract
The invention discloses a preparation method of all-trans beta-carotene. The carotene cis-trans isomer mixture is subjected to isomerization reaction under the conditions of nitrogen and light protection in the presence of a catalyst and an auxiliary agent to obtain the all-trans beta-carotene, wherein the catalyst is a platinum or ruthenium complex. The method has the advantages of short isomerization time, low temperature, high all-trans content of the product and good isomerization effect on a wider range of cis-trans isomer mixture.
Description
Technical Field
The invention relates to the field of synthesis of all-trans beta-carotene, in particular to a method for preparing all-trans beta-carotene through isomerization reaction
Background
beta-Carotene (beta-Carotene, molecular formula C) 40 H 56 The structure is shown as the following formula) is a precursor of vitamin A, commonly called provitamin A, and is the carotenoid which attracts people's attention for the first time. Beta-carotene is an antioxidant, has a detoxifying effect, and is an indispensable nutrient for maintaining human health. In addition, beta-carotene has significant functions in anticancer, cardiovascular disease prevention, cataract prevention, and prevention of various degenerative diseases caused by aging and aging. Therefore, the method is widely applied to industries such as medicine, food, cosmetics, feed additives, dye and the like, and has good market prospect.
Beta-carotene has a long-chain conjugated double bond structure, so a large number of cis-trans isomers exist, and different isomers have different physical and chemical properties. Wherein, the thermal stability and the chemical stability of the all-trans isomer are superior to those of other cis isomers. In terms of nutritional value, the VA activities of the 13-cis and 9-cis isomers are 53% and 38% of the all-trans form respectively. And the all-trans bioavailability is higher than that of the cis isomer. Therefore, in the process of producing beta-carotene, it is an effective way to maintain its biological potency to prepare beta-carotene as an all-trans isomer as much as possible.
Several known methods have been previously reported for the preparation of all-trans beta-carotene.
US2849507 reports that 100g 15-cis-beta-carotene isomerizes in 500ml petroleum ether with a boiling range of 80-100 ℃ for 10 hours at 80 ℃ to yield 95-97g all-trans beta-carotene. Ethyl acetate is used to replace petroleum ether for isomerization, and 90g of all-trans beta-carotene can be obtained. The method has low yield and long isomerization reaction time, and is not beneficial to large-scale production. In addition, whether the method mainly takes 15 cis and derivatives thereof as substrates or not has universality to be examined.
US 399757 reports isomerization of 500g of a reaction crude product with a solids content of 44.2% in 2.5L of water at 100 ℃ for 20h to obtain 133.9g of all-trans beta-carotene after work-up. The method has high isomerization temperature, long time and low yield. Meanwhile, the post-reaction treatment is complicated, and large-scale production is not facilitated.
CN1935789 reports that a mixture of beta-carotene isomers is put in a high-boiling point and low-toxicity solvent to react for 10-30h to obtain all-trans beta-carotene. The method has high reaction temperature and long reaction time. And there is no mention of the cis isomer content of the starting materials for which the process is applicable.
In conclusion, the existing method for preparing all-trans beta-carotene by isomerization reaction has the defects of high reaction temperature, long reaction time, low reaction yield or purity, limitation on the content and variety of cis-isomers in the initial reactant and the like.
Disclosure of Invention
In view of the above problems in the prior art, the present invention aims to provide a method for preparing all-trans beta-carotene. The method has the advantages of short isomerization time, low temperature, high all-trans content of the product and good isomerization effect on a wider range of cis-trans isomer mixture.
In order to achieve the purpose, the technical scheme adopted by the invention is as follows:
a preparation method of all-trans beta-carotene comprises the following steps:
carrying out isomerization reaction on the carotene cis-trans isomer mixture under the conditions of nitrogen and light protection in the presence of a catalyst and an auxiliary agent to obtain all-trans beta-carotene;
the catalyst is a platinum or ruthenium complex.
In the carotene cis-trans isomer mixture, the cis-isomer accounts for 0-80%, preferably 10-75% by taking the total mass of the cis-isomer and the trans-isomer as 100%;
preferably, the carotene cis-trans isomer mixture has a purity of more than 90% based on the total mass of cis-isomer and trans-isomer, can be purchased directly or prepared by any known method.
The platinum or ruthenium complex is selected from any one or combination of at least two of tetrakis (triphenylphosphine) platinum, trans-diammine dichloroplatinum, cis-dichlorobis (triphenylphosphine) platinum, cisplatin, tris (triphenylphosphine) ruthenium dichloride, ruthenium trichloride, hexamine ruthenium chloride and dichlorodicarbonyl bis (triphenylphosphine) ruthenium, and is preferably hexamine ruthenium chloride;
preferably, the catalyst is used in an amount of 0.05 to 0.25wt%, preferably 0.1 to 0.2wt%, based on the mass of the mixture of carotenes cis-trans isomers.
The auxiliary agent is selected from pyridine, quinoline and derivatives of pyridine and quinoline, preferably any one or combination of at least two of 4-ethylpyridine, 4-methoxypyridine, 2-methylaminopyridine, quinoline-8-formaldehyde, quinoline-8-sulfonic acid, 2-chloroquinoline and 5-nitroquinoline, and more preferably 2-chloroquinoline;
preferably, the amount of auxiliaries is from 2 to 10% by weight, preferably from 5 to 8% by weight, based on the mass of the catalyst.
The isomerization reaction is carried out at the reaction temperature of 20-120 ℃, preferably at the reaction temperature of 40-80 ℃; the reaction time is 3 to 10 hours, preferably 5 to 8 hours.
The isomerization reaction is preferably carried out in a solvent environment, and the solvent is a ketone solvent, preferably cyclohexanone, isophorone or a solvent with a general formula of R 1 COR 2 Ketones of (2), wherein R 1 、R 2 Each independently a straight or branched alkyl group of carbon number 1 to 3, more preferably butanone;
preferably, the isomerization solvent is used in an amount of 2 to 8 times, preferably 3 to 5 times, the mass of the mixture of cis-trans-isomers of carotene.
After the isomerization reaction, the method also comprises the post-treatment processes of cooling, suction filtration, drying and the like, is conventional operation in the field, and has no special requirement.
According to the method for preparing the all-trans beta-carotene through the isomerization reaction, the selectivity of the isomerization reaction can reach more than 99%, the yield of the isomerization reaction is not lower than 98%, and the content of the all-trans isomer in the product is not lower than 98.5%.
The technical scheme of the invention has the following advantages:
(1) Aiming at the isomerization reaction of beta-carotene, the isomerization reaction of the carotene can be carried out at a lower temperature under the catalytic action of the platinum or ruthenium complex, the isomerization time is greatly shortened, the reaction operation simplicity is improved, and the method is favorable for large-scale production.
(2) The method has good isomerization effect on the isomer mixture with wide range of cis-inverse ratio, and the maximum ratio of the cis-isomer can reach 80 percent.
(3) The isomerization catalyst can perform a side reaction of hydrogen transfer with the ketone solvent while catalyzing the isomerization reaction, thereby reducing the yield and the purity of the product. The auxiliary agent is a poisoning agent, and can poison the catalyst and reduce the activity of the catalyst, so that the selectivity of the isomerization reaction is improved, and the reaction yield and the product purity are ensured to be in the range.
Detailed Description
The present invention will be described in further detail with reference to the following examples, which are not intended to limit the scope of the invention. The reagent of the present invention is purchased from national pharmaceutical group chemical reagents, ltd, unless otherwise specified.
Raw materials of cis-trans isomers of beta-carotene: preparation method reference document analysis of beta-Carotene by-product during Heat treatment method (food science, revenge, chenyirong, lihaorang) weighing beta-Carotene product (96 wt% purity, 94wt% cis isomer, from Xinhe company Limited) about 50mg, placing in 50ml brown round bottom flask, heating in oil bath at 175 deg.C under high vacuum for 10-60min, rapidly placing the flask in ice water for cooling, and taking out the solid;
the starting materials of the desired purity and isomer ratios of examples 1-5 were prepared by adjusting the heating time in a 175 deg.C oil bath under high vacuum.
And (3) liquid chromatography characterization: agilent 1260 type liquid chromatograph, chromatographic column Sphersorb C18 column
An ultraviolet visible light splitting detector Hitachi L7420 and a chromatographic workstation data processing system Chomatopac C-RIA with the flow rate of 1mL/min and the wavelength of 455nm.
Note: the isomerization reaction yield in the examples is product mass product purity/(starting material mass initial purity); the product purity is the total content of cis-isomer and trans-isomer, based on the product mass as 100%.
Example 1
100g of cis-trans-isomer of beta-carotene (purity 90%, cis-isomer ratio 80%), 0.1g of hexamine and ruthenium chloride, 0.005g of 2-chloroquinoline, and 400g of butanone were charged into a 1L three-necked flask. Reacting for 8 hours at 50 ℃ under the protection of nitrogen and in the dark. Cooling to room temperature, filtering, and drying. 89.5g of the product is obtained, the purity of the product is 99.5%, the HPLC all-trans content accounts for 99.0%, the isomerization selectivity is 99.5%, and the isomerization yield is 98.9%.
Example 2
100g of cis-trans isomer of beta-carotene (purity 95%, cis-isomer content 10%), 0.05g of ruthenium hexammoniachloride, 0.001g of 2-chloroquinoline and 300g of butanone were added to a 1L three-necked flask. Reacting for 3 hours at 50 ℃ under the protection of nitrogen and in the dark. Cooling to room temperature, filtering, and oven drying. 94.33g of product is obtained, the purity of the product is 99.3%, the HPLC all-trans content accounts for 98.8%, the selectivity of the isomerization reaction is 99.2%, and the yield of the isomerization reaction is 98.6%.
Example 3
100g of cis-trans isomer of beta-carotene (purity 92%, cis isomer content 60%), 0.25g of ruthenium hexammoniachloride, 0.025g of 4-methoxypyridine and 800g of 2-pentanone were added to a 2L three-necked flask. Reacting for 10 hours at 80 ℃ under the protection of nitrogen and in the dark. Cooling to room temperature, filtering, and drying. 91.45g of the product is obtained, the purity of the product is 99.4%, the HPLC all-trans content accounts for 98.6%, the selectivity of the isomerization reaction is 99.3%, and the yield of the isomerization reaction is 98.8%.
Example 4
100g of a β -carotene cis-trans isomer (94% purity, 35% cis-isomer content), 0.15g of ruthenium dichloride, 0.005g of 2-chloroquinoline, and 500g of 3-pentanone were added to a 1L three-necked flask. Reacting for 5 hours at 60 ℃ under the protection of nitrogen and in the dark. Cooling to room temperature, filtering, and oven drying. 93.15g of the product is obtained, the purity of the product is 99.2%, the content of HPLC all-trans is 98.5%, the selectivity of the isomerization reaction is 99.0%, and the yield of the isomerization reaction is 98.3%.
Example 5
100g of a cis-trans-carotene isomer (having a purity of 94% and a cis-isomer content of 30%), 0.20g of trans-diamminedichloroplatinum, 0.020g of quinoline-8-carbaldehyde and 400g of isophorone were added to a 1L three-necked flask. Reacting for 3 hours at 120 ℃ under the protection of nitrogen and in the dark. Cooling to room temperature, filtering, and oven drying. 93.05g of the product is obtained, the purity of the product is 99.0 percent, the HPLC all-trans content is 98.5 percent, the selectivity of the isomerization reaction is 99.0 percent, and the yield of the isomerization reaction is 98.0 percent.
Comparative example 1
With reference to example 1, the only difference is that: the reaction process is carried out without the addition of 2-chloroquinoline and the other operations are the same as in the examples. 88.44g of the product is obtained, the purity of the product is 98.0 percent, the HPLC all-trans content accounts for 97.6 percent, the selectivity of the isomerization reaction is 97.5 percent, and the yield of the isomerization reaction is 96.3 percent.
Comparative example 2
Referring to example 1, except that no catalyst, ruthenium hexaammine chloride, was added during the reaction, the other operations were the same as in example. 89.05g of the product is obtained, the purity of the product is 95.2%, the HPLC all-trans content accounts for 86.2%, the isomerization selectivity is 99.2%, and the isomerization yield is 94.2%.
Comparative example 3
With reference to example 1, the only difference is that: the same procedure as in example was repeated except that 0.005g of 2-chloroquinoline was replaced with 1-chloronaphthalene of an equivalent mass. 88.34g of the product is obtained, the purity of the product is 97.8 percent, the HPLC all-trans content accounts for 97.5 percent, the selectivity of the isomerization reaction is 97.6 percent, and the yield of the isomerization reaction is 96.0 percent.
Comparative example 4
With reference to example 1, the only differences are: the catalyst ruthenium hexammine chloride was replaced with palladium acetate of equal mass, and the other operations were the same as in the examples. 89.62g of the product is obtained, the purity of the product is 94.9%, the HPLC all-trans content accounts for 88.8%, the selectivity of the isomerization reaction is 99.0%, and the yield of the isomerization reaction is 94.5%.
Comparative example 5
With reference to example 1, the only difference is that: the solvent butanone was replaced with glycerol of equal mass, and the other operations were the same as in the examples. 88.33g of the product is obtained, the purity of the product is 96.9 percent, the HPLC all-trans content accounts for 96.0 percent, the selectivity of the isomerization reaction is 98.0 percent, and the yield of the isomerization reaction is 95.1 percent.
Claims (17)
1. A preparation method of all-trans beta-carotene is characterized by comprising the following steps:
carrying out isomerization reaction on the carotene cis-trans isomer mixture under the conditions of nitrogen and light protection in the presence of a catalyst and an auxiliary agent to obtain all-trans beta-carotene, wherein the catalyst is a platinum or ruthenium complex;
the platinum or ruthenium complex is selected from any one or the combination of at least two of tetrakis (triphenylphosphine) platinum, trans-diammine dichloroplatinum, cis-dichlorobis (triphenylphosphine) platinum, cisplatin, tris (triphenylphosphine) ruthenium dichloride, ruthenium trichloride, hexamine ruthenium chloride and dichlorodicarbonyl bis (triphenylphosphine) ruthenium;
the auxiliary agent is selected from pyridine, quinoline and derivatives of the pyridine and the quinoline;
the isomerization reaction is carried out in a solvent, and the solvent is a ketone solvent.
2. The method as claimed in claim 1, wherein the mixture of cis-trans isomers of carotene has a cis-isomer ratio of 0-80% based on 100% by mass of the total of the cis-isomer and the trans-isomer.
3. The method of claim 2, wherein the cis isomer is present in a proportion of 10 to 75%.
4. The method according to claim 2, wherein the carotene cis-trans isomer mixture has a purity of 90% or more based on the total mass of cis-isomer and trans-isomer therein.
5. The process of claim 1, wherein the platinum or ruthenium complex is ruthenium hexaammine chloride.
6. The method as claimed in claim 1, wherein the catalyst is used in an amount of 0.05 to 0.25wt% based on the mass of the mixture of cis-trans-isomers of carotene.
7. The method as claimed in claim 6, wherein the catalyst is used in an amount of 0.1 to 0.2wt% based on the mass of the mixture of the carotenes cis-trans isomers.
8. The method according to claim 1, wherein the auxiliary agent is any one or a combination of at least two of 4-ethylpyridine, 4-methoxypyridine, 2-methylaminopyridine, quinoline-8-carbaldehyde, quinoline-8-sulfonic acid, 2-chloroquinoline, and 5-nitroquinoline.
9. The method according to claim 8, characterized in that the auxiliary agent is 2-chloroquinoline.
10. The process according to claim 1, wherein the promoter is used in an amount of 2 to 10wt% based on the mass of the catalyst.
11. The process according to claim 10, wherein the promoter is used in an amount of 5 to 8wt% based on the mass of the catalyst.
12. The process according to claim 1, wherein the isomerization reaction is carried out at a temperature of 20 to 120 ℃ for a time of 3 to 10 hours.
13. The process according to claim 12, wherein the isomerization reaction is carried out at a temperature of 40 to 80 ℃ for a time of 5 to 8 hours.
14. The process of claim 1, wherein the ketone solvent is cyclohexanone, isophorone or compounds of formula R 1 COR 2 Ketones of (2), wherein R 1 、R 2 Each independently is a linear or branched alkyl group having 1 to 3 carbon atoms.
15. The method according to claim 14, wherein the ketone solvent is butanone.
16. The process according to claim 1, wherein the amount of the isomerization solvent is 2 to 8 times the total mass of the mixture of cis-trans isomers of carotene.
17. The process according to claim 16, wherein the amount of the isomerization solvent is 3 to 5 times the total mass of the mixture of cis-trans isomers of carotene.
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| US2849507A (en) * | 1954-12-24 | 1958-08-26 | Hoffmann La Roche | Preparation of all-trans-carotenoid compounds |
| US4051174A (en) * | 1973-08-21 | 1977-09-27 | Hoffmann-La Roche Inc. | Isomerization process |
| KR100263542B1 (en) * | 1997-12-05 | 2000-08-01 | 윤재천 | Process for the isomerization and reinement of beta-carorene |
| CN100484919C (en) * | 2006-10-19 | 2009-05-06 | 浙江大学 | Method for preparing full-trans beta-carrotin |
| CN111004163B (en) * | 2019-11-13 | 2021-12-10 | 万华化学集团股份有限公司 | Method for catalyzing vitamin A isomerization by ruthenium catalyst |
| CN112354537A (en) * | 2020-11-03 | 2021-02-12 | 万华化学集团股份有限公司 | Preparation and application of modified palladium-carbon catalyst, and vitamin A cis-trans isomer conversion method |
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